Process of producing resinous products from acetylene and secondary and tertiary alkyl phenols



Patented Jan. 11, 1949 UNITED OFF ICE] rnocnss or rnonocmc; nnsmoos mon-'UCTS FROMACETYEENE ANDSECONDARY A'N-D TERTIARYIALKYIEAPHENOLS' Abraham0.- Zoss,. .-Easton, ,:Ba., .assignorl to General. Aniline: &-; FilmCorporation, New York; N. Y., a corporation of Delaware.

NoDrawing. applicanonmamheo,194's, SerialiNo. 65835881 of resinousproducts, from secondary and tertiary alkyl-substituted phenols andacetylene.

Valuable resinous products. have heretofore been produced by condensingacetylene with various phenols, including tertiary alkyl-vsube stitutedphenols at superatmosphericpressures and temperatures of from 100to-about 300? C. the presence of zinc or cadmium salts of organiccarboxylic acids or of organic nitrogenous ibases such as amines ascatalysts. Theseprocassesare described in U. srPatents Nos. 2.,027,'199=.and 2,072,825 to Reppe et al. Itwas believed,. how.- ever, that thezincor cadmiumsaltspforganic carboxylic acids and the organicnitrogenous bases were unique in their action ascatalystsand wereessential if resinous products werelto-be obtained.

I have now found that valuable resinous-prod ucts having propertiesquite similar to those-obtained by the above mentioned procedures can beobtained in the case of secondary; and; tertiary alkyl-substitutedphenols by causing acetylenesto act on such secondary or tertiary;alkylzphenols at temperatures within the rang-eof 150.4100. C. andpreferably in the range-of 200-250? C. and

under superatmospheric.pressureJin the presence of 1-20% and preferably1-5% of an alkali metal compound having a strongly alkaline reaction.

The catalysts which I employ. arelthe: alkali metal oxides, hydroxidesand the likewhich'; with the phenol employed, will form a vphenolate. Ifdesired, the catalysts employed may, be'employed. in the form of apre-formed phenolate or1alcoholate. Examples of suitable catalysts are.the: oxides, carbonates and hydroxides of the; alkali metals, e. g.,sodium, potassium, lithium, rubidium and cesium, or their alcoholateswith such alcohols as methanol, ethanol, propanoh butanol and the like,or the phenolate of the alkalimetals with any of the secondary or.vtertiary phenols mentioned above or other phenolic compounds, forinstance, phenol or cresols.

For the production of valuable resinous, prod-- ucts in accordance withthe present invention, I have found those phenolic compounds whichcontain a secondary or tertiary alkyl group as a substituent and whichare unsubstituted in two of the positionsortho and para-to a hydroxylgroup to be suitable. As specific examples of such secondary andtertiary alkyl phenols may be mentioned oand p-isopropyl phenol, oandpsecondary and tertiary butyl phenols, oand p-cyclohexyl phenol, oandp-secondary octyl phenols, oand p-(1,1,3,3-tetramethylbutyl)- 21 phenol,.o and p-secondary and tertiary amyl phenols o- .and p-secondary andtertiary nonyl phenols and ol-and. p-secondary and tertiaryvdodecyllphenols. I particularly prefer the monosubstituted tertiaryalkylphenolic compounds ob tained bycondensing. phenol with an olefine or atertiaryalkyl- :halide or alcohol containing, from 3. to about 12.carbon atoms. In place of the phenols mentioned above, there may alsobeemployed the corresponding secondary and tertiary alkyl substitutedmeta-cresolsi Itis also possible to -obtain. valuable resinous productsemploying the secondary and tertiary alkyl substituted re;-

sorcinols. However, when. d-ihydroxy; phenolic compounds ;are-.employed, the resinous products obtained are generally somewhat more;infusible and insoluble than is the'case when the alkyl gem hydrogen,methane-,. ethane andthe like, in

order to; preclude. the possibility of explosion-.; Whenydilutedlwithxsuch inert' gases in: the ration,

oftaboutiz to:3-- parts of inertgas tol' partr-of acetylene; a-pressurewithin the range. ofv -300- poundswper: square. inch is required in 1order for;

a satisfactory; rat'epof reaction? to. be; obtained. However;;. asdisclosed in copending application ofilBellerg-flhrist and. Wuerth,Serial No. 621,620; byqcarbureting ;the-.acetylene with: a normalliquid.

inertiorganicdil-uent.suchas cyclohexanesor mix-- tures, of isaturatedhydrocarbons; such as occur:

in petroleum fractions, a substantially smaller amount of diluent may beemployed and reaction carried out at a lower pressure and/ortemperature. The exact pressure to be employed will therefore varysomewhat with the particular diluent employed. In general, however, thepressure will be such that the partial pressure of the acetylene will befrom about 2 to about 8.5 atmospheres.

tanning agents, cation exchange resins and By varying the amount ofcatalysts and relative proportions of acetlyene and phenols, thetemperature of reaction and selection of particular secondary ortertiary alkyl phenols, resinous products having a wide variety ofproperties and varying from viscous to semi-hard or hard products may beobtained. Likewise, resinous products having varying solubilities fromreadilysoluble to partly-soluble or only capable of swelling in organicsolvents such as acteone, methanol} ethanol, diethylether, benzene,'xylene and the like Y may be obtained. The resinous products obtainedin accordance with the present invention are selected from the classconsisting of secondary and tertiary alkyl groups containing 3 to 12carbon atoms, but which are free of substituents other than alkyl groupsand which are unsub- "stituted in two of the positions ortho and para toa hydroxy group, in the presence of a strongly similar to those obtainedunder similar conditions as regards the phenol employed, the temperatureand ratio of acetylene to phenol in the processes disclosed in theabove-mentioned U. S. Patents Nos. 2,027,199 and 2,072,825. Depending ontheir,

properties, they may be employed eitherdirectly' or after subsequentpurification as tackifiers for natural and synthetic rubbers and in thepreparation of lacquers, varnishes, insulating agents, adhesivecompositions and the like. In some of these preparations, the resinousproducts may be mixed with fillers, such as carbon black, pigments anddyes. They are also compatible with a wide variety of other natural andsynthetic resins and waxes and make valuable modifiers for suchproducts.

, The resinous products may also be sulphonated, if desired, in order toobtain valuable synthetic the like.

The following example (in which the parts are by weight) illustrates atypical preferred embodiment of this invention: a

Example 500 parts of p-tertiary butyl phenol and 8 parts of potassiumhydroxide were charged into a pressure vessel having an efiicientstirrer. Air-was removed by purging with nitrogen and the charge in thereactor was then heated to 210 C., nitrogen being admitted until theinternal pressure was 145 pounds per square inch. Acetylene was thenadded until a total pressure of 200 pounds per square inch was obtainedand the reaction mass was maintained at 210 C. and under a pressure of200 pounds per square inch by the continuous addition of acetylene for24 hours. period, 145 parts of acetylene were added. The reaction masswas then cooled and the pressure released. There was thus obtained aresinous product having a molar ratio of p-tertiary butyl phenol toacetylene of 1:0.96. This material had a molecular weight of about 600and a Ubbelohde drop point of 116.5" C, It was soluble in methanol,ethanol, acetone, benzene, cyclohexane, petroleum ether, ethyl acetate,diethyl ether, normal butanol and it was found to be particularlyvaluable as a tackifier for natural and synthetic rubbers.

- By substituting p-tertiary amyl phenol or p-(1,1,3,3-tetramethylbutyl)phenol for the p-tertiary butyl phenol in the above example, similarproducts which are valuable as tackifiers for natural and syntheticrubbers may be obtained. Y

During this alkaline-reacting alkali metal compound as a catalyst;

, 2. Thev method, of producing resinous condensation products, whichcomprises causing acetylene to act at a temperature between 200 and 250C. and at a superatmospheric pressure on a compound selected from thegroup consisting of phenols and cresols having an alkyl substituentselected from the class consisting of secondary and tertiary alkylgroups containing 3 to 12 carbon atoms, but which are free ofsubstituents other than alkyl groups and which are unsubstituted in twoof the positions ortho and para to a hydroxy group, in the presence of astrongly alkaline-reacting alkali metal compound as a catalyst.

3. The process of producing resinous condensation products, whichcomprises causing the non-explosive mixture of acetylene and an inertgas to react at a temperature of to 300 C. and at such pressure that thepartial pressure of acetylene is from about 2 to about 8.5 atmosphereson a compound selected from the group consistin of phenols and cresolshaving an alkyl substituent selected from the class consisting ofsecondary and tertiary alkyl groups containing from 3 to 12 carbonatoms, but which are free of substituents other than alkyl groups andwhich are unsubstituted in two of the positions ortho and para to ahydroxy group, in the presence of a strongly alkaline-reacting alkalimetal compound as a catalyst.

4. The process as defined in claim 1, wherein the alkyl phenol isp-tertiary butyl phenol.

5. The process as defined in claim 2, wherein the alkyl phenol isp-tertiary butyl phenol.

6. The process as defined in claim 3, wherein the alkyl phenol isp-tertiary butyl phenol.

' 7. The process as defined in claim 3 wherein the alkyl phenol isp-tertiary amyl phenol.

8. The process as defined in claim 3 wherein the alkyl phenol isp-(1,1,3,3-tetramethylbutyl) The following references are of record inthe file of this patent:

UNITED STATES PATENTS N umber

